Vat dyestuffs derived from aceanthrenequinone and process of preparing them



Patented June 30., 1936 UNITED STATES PATENT o icEi VAT 'DYESTUFFSDERIVED FROM'ACEAN- THRENEQUINONE AND PROCESS OF PRE- PARING THEMWilhelm Eckert and Heinrich Sieber, Frankforton-the-Main -Hochst,Germany, assignors to General Aniline Works, Inc., New York, N. Y., acorporation, of Delaware No Drawing. Application June 10, 1933, SerialNo. 675,331. In Germany June 14, 1932 13 Claims. (01. 260-29) I (2) 30parts of the condensation product from The present invention relates tovat dyestufls and to a process of preparing them. 7

We have found that new vat dyestufis are obtainable by melting with acaustic alkali a compound which is obtainable by condensing anaceanthrenequinone with a 1,2-diamino-compound and which has the generalprobable formula:

tho 1 are introduced at about G. into a mixture of 100 parts of causticpotash and '70 parts of alcohol. The temperature is gradually raised toC. to C. and maintained for about half an hour. The reaction mass isthen poured into water, the dyestufl which has been precipitated,

is filtered by suction, washed until neutral and dried. It forms agreen, amorphous powder which is very. difficultly soluble in the usualorganic solvents. It dissolves, in concentrated sulfuric acid to anolive solution. The dyestufi dyes cotton from a green vat green tints ofvery good fastness properties. V

(4) Methyl -,aceanthrenequinone I from Z-methylanthracene andoxalylchloride) "is i aceanthrenequinone with 2-chlcro-4,5diamino'-toluene, which corresponds to one of the follow ing formulae or which isa mixture'of the prod ucts of the following formulae:

are introduced into a mixture of 200 parts of caustic'potash and 200parts by volume of alcohol and the whole is heated at150 C. to 160 C.The color of the mass turns green, while the mass froths; After 20minutes the formation of the dyestuff is finished. The mass -is dilutedwith 7 water and "worked up in known manner. The dyestuff thus obtaineddyes cotton green tints.

(3) Aceanthrenequinone may easily be con,-

densed with: ethylene-1,2-diamine .in alcohol to form an azine of thefollowing, constitution:

The saidazine is molten in a manner analogous to that described inExamples 1 or 2, to formav green vat dyestufi which dyes cotton greentints of a bluish hue;

' (obtainable condensed to an azine-by heating in glacial acetic acidwith 1,2-diamin0benzene. '10 p.arts of the said condensation product aremelted at 150 0'. to C. with-10o parts of'caustic potash and '70 partsof alcohol. The formation V The yield is nearly quantitative.

of the dyestuif is finished after half an hour.

j The dyestufi dyes cotton from'ia green vat green tints.

() By treating the condensation product from i aceanthrenequinone and1-methy1 3A-diamino-" benzene which corresponds to one of "the follow?ing formulae or which containsproducts ofv both formulae; 7

vat dyestuif is obtained. I a (6);.6 parts of the dyestufi 'as it isobtained 7 according to'Example l, are suspended-inasfine a form aspossible in '70 parts by volumeof nitrobenzene. In the course of bromineare gradually at 40 C. to Csand the whole is maintained twohours 35parts of dropped ingwhile stirring,

' at this temperature ior further 5 hours; The

" K to boiling for 2 to 3 hours with 21 parts of 1,2-di

. 1 amino-naphthalene (hydrochloride) 230 parts by volume of pyridine.The azine thusxformed introducedat about C into a melt consisting ofabout parts of. caustic potash and 70 parts 'p by volume of alcohol andthe temperature is raised to about C. When the fonnationof men isallowed ,to'

. 1bromination product thus {by suction, the solid matter is washed withal.- cohol and subsequently with Water-and dried.

formed is then filtered The dyestufi dyes cotton green tints having a"purer shade than the dyeings obtained by rnwns of the, startingmaterial. (7). 23 parts of aceanthrenequirione are heated whichcorresponds with one of. the following formulae or which is a mixtureof. the products Q. offthe following formulae:

is filteredby suction, 'washed with pyridine and subsequently withwater.

20 parts of the said condensation product are the dyestuff is finished,.'the cool and diluted with water. The dyestuff. thus precipitated isfiltered by suction, washed with water until neutral and dried. It formsa dark green, powder which dissolves in concentrated sulfuric acid to aviolet solution. It melts at above 300 0.; it is very d iflicultlysolub1e .in the 1 usual'organic solvents, even in -the heat. 7 r

V (8) By melting --under the same or similar L conditions thecondensation product'from aceanthrenequincne which corresponds with oneof 'the following and '2,3-diamino-.fluorenone in 'a manner as describedin Example 1, a greenj The dyestuff .dyes cotton rfrom agreenvat clearyel-lowish-green tints. oi very' good, Jfastness :PI P Ities formulae orwhich is a mixture of theproducts of the following formulae:

with caustic'potash and alcohol, a dyestuffis obtained the dyeings ofwhich have amore' bluish tint than those of ample'k We claim:

'I'heprocess which com-prises melting with a caustic alkali a-compoundwhich isobtainable by i aceanthrenequinone with a 1,2

.d-iarnino compound and whichhas the general:

condensing an formula;

wherein N-RN V p 7 radical, B being a radical ofthealiphatic, benzene,"naphthalene and fluorene series.

2 The process hich comp fses melting with-a caustic alkali" a compoundwhich is obtainable by aceanthrenequinone with 'a 1,2

condensing an the dyestuff described in Err- -20 I ansfthe1',2-diaminodiamino compound' and-which has the general i rm lw radical,R being a 1'ad'ical of the aliphatic, ben-' zene, naphthalene'andfluorene series and halogenating the compound tnus obtained.

3. The process which comprise's melting with a caustic alkali acompoundwhich is obtainable by condensing an acea'nthreneduinone with anorthofdiamino compound of the benzene series; and which has the generalformulaz .w .N-.- ne se Yli ea radical, Rh'ei ng aradical of thebenzeneseriesg 1 4. 'Theprocesswhich comprises melting with a,

caustic alkali a compound whichis' obtainable-by V condensing anaceanthrenequinonewith' an or tho-diamino compound of thebenzenes'eri'es and which has the general formula:

general formula:

wherein =NRN= means the 1,2-diaminoradical, R being a radical of thebenzene series.

6. The process which comprises melting at about C. to about 170 C. withpotassium hydroxide in the presence of ethyl alcohol a compound which isobtainable by condensing an aceanthrenequinone with anortho-diamino-compound of the benzene series and which has the generalformula:

wherein =NRN= means the 1,2-diaminoradical, R being a radical of thebenzene series, and halogenating the compound thus obtained.

'7. The process which comprises melting at about 150 C. to about C. withpotassium hydroxide in the presence of ethyl alcohol a compound which isobtainable by condensing aceanthrenequinone with 1,2-diaminobenzene andwhich has the formula:

8. The process which comprises melting at about 150 C. to about 160 C.with potassium hydroxide in the presence of ethyl alcohol a compoundwhich is obtainable by condensing aceanth-renequinone with1,2-diaminobenzene and which has the formulax' isolating the dyestufithus obtained and treating its suspension in nitrobenzene with bromineat about 40 C. to about 50 C.

9. The compounds substantially identical with those which are obtainableby the process which comprises melting with a caustic alkali a compoundwhich is obtainable by condensing an aceanthrene with a 1,2-diaminocompound and which has the general formula:

A: tha

OiO

wherein =N--R-N= means the 1,2-diaminoradical R being a radical of thealiphatic, benzene, naphthalene and fiuorene series. I

10. The compounds substantially identical with those which areobtainable by the process which comprises melting with a caustic alkalia compound which is obtainable by condensing an' aceanthrenequinone witha 1,2-diamino compound and which hasthe general formula:

N ha! wherein =N-R--N= means the 1,2-diaminoradical, R being a radicalof the aliphatic, benzene, naphthalene and fiuorene series and.halogenating the compound thus obtained.

11. The compound substantially identical with that which is obtainableby the process which comprises melting at about 150 C. to about 160 7 C.with potassium hydroxide in the presence of ethyl alcohol a compoundwhich is obtainable by condensing aceanthrenequinone with1,2-diamino-benzene and which has the formula:

forming a green amorphous powder being very difiicultly soluble in theusual organic solvents, dissolving in concentrated sulfuric acid to anolive solution and dyeing cotton from a green 75 vat green tints of verygoodfastness properties 12. The compound substantially identical with vj that which is obtainable by the process which comprises melting atabout 150C. to about 160 C;

' 'with potassium hydroxide in the presence of ethyl alcohol a compoundwhich is obtainable by condensing aceanthrenequinone with1,2-diaminobenzene and which has the formula:

isolatingthe d s uirr thus obtained and treating its suspension innitrobenzene with'bromine at about 40 C. to about 50 C., said'compoundbeing a dyestuff'dyeing cotton'clear green tints of very goodfastness'properties. a

13. The compound substantially identical with that which is obtainableby the process which comprises melting at; about 1'10? with potassiumhydroxide in the presence ,of ethyl alcoh ol a compound which isobtainable by condensing aceanthrenequinone thalene and which: has theformula:

with 1,2-diamino-naphor is a mixture of compounds of these formulae,

7 forming a green powder which" dissolves in concentrated sulfuric acidto a violetsolution and dyeing iroma green vatcottongclearyellowishgreen tints of very good fastness properties.

VWILI-IELM ECKERT. HEINRICH SIEBER;

